Note: Descriptions are shown in the official language in which they were submitted.
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
LIQUID GEL AUTOMATIC DISHWASHING DETERGENT
COMPOSITION COMPRISING ANHYDROUS SOLVENT
Technical field
The present invention is in the field of dishwashing, in particular it relates
to dishwashing
and automatic dishwashing products, auxiliaries and methods suitable for
cleaning soiled
dishware, glassware, cookware and tableware.
Background of the invention
The following references relate to the use of solvents in the automatic
dishwashing
context: JP-A-10,017,900; JP-A-11,117,000; and WO 02/16222 Al. Fox example, JP-
A-
10,017,900 discloses an automatic dishwashing auxiliary composition comprising
non-ionic low
foaming surfactant, organic solvent and water. The composition allegedly
delivers detergency
and drying benefits. JP-A-11,117,000 discloses a cleaning assistant
composition for automatic
dishwashing machines comprising surfactant, organic high-molecular
polyelectrolyte, water-
soluble solvent and water. WO 02/16222 A1 discloses water-soluble containers
containing
aqueous compositions that can comprise greater than 3% free water, surface
active agents,
enzymes, co-builder, organic solvents and co-solvents, dyes, and colourants.
The following references relate to the use of non-aqueous solvents in the
automatic
dishwashing context: U.S. Patent No. 4,753,748; U.S. Patent No. 5,094,771;
U.S. Patent No.
5,164,106; U.S. Patent No. 5,169,553; U.S. Patent No. 5,240,633; U.S. Patent
No. 5,318,715;
U.S. Patent No. 5,510,048; U.S. Patent No. 5,527,483; U.S. Patent No.
5,545,344; U.S. Patent
No. 5,618,465; U.S. Patent No. 6,228,825 B1; EP. Patent No. 0611206; and WO
00/75272. For
example, U.S. Patent No. 4,753,748 discloses concentrated, stable, non-
settling liquid detergent
compositions comprising sodium tripolyphosphate and a water content of about
1%. U.S. Patent
No. 6,228,825 B 1 discloses a non-aqueous liquid automatic dishwashing
composition disposed in
a water-soluble package comprising an organic solvent, an alkali metal
phosphate builder salt, a
non-ionic surfactant, a silicate, an alkali metal non-phosphate builder salt,
and an antiredeposiiton
agent. The composition delivers a dosable composition.
The problem with non-aqueous solvent compositions is that when these
compositions are
placed in water-soluble pouches for use in automatic dishwashing applications,
the pouches tend
to swell during storage. This is believed to be due mainly to moisture uptake
by the anhydrous
solvent composition via mass transport through the pores of the pouch.
Consequently, the water-
soluble pouches become swollen and tight to the touch. Their appearance and
feel is not
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
appealing to consumers. Furthermore, the types of dyes, pigments and colorants
that are
generally available for non-aqueous solvent compositions are generally limited
to water insoluble
dyes, pigments and colorants which tend to limit the color selection of the
non-aqueous solvent
compositions to drab coloration which also makes the water-soluble pouches
less appealing to
consumers. Thus, there is a need for pouched products containing anhydrous
solvents that avoid
excessive pouch swelling. There is also a need for automatic dishwashing
cleaning products
comprising anhydrous solvent compositions in water-soluble pouches that
provide more pleasing
color aesthetics.
Therefore, it is desirable to provide a liquid gel anhydrous organic solvent
composition
that minimizes excessive pouch swelling and is pleasing to the touch, while at
the same time,
provides superior product color aesthetics to the consumer by controlling the
free water content
of the composition by using hydrated sodium tripolyphosphate and selecting
pleasing water-
soluble dyes.
SUMMARY OF THE INVENTION
The present invention provides a liquid gel anhydrous organic solvent
composition
comprising sodium tripolyphosphate hexahydrate to control the free water
content of the
composition which allows the use of water-soluble dyes and reduces the effect
of pouch swelling.
In one aspect of the present invention, an organic solvent composition
suitable for use in
automatic dishwashing is provided. In one non-limiting embodiment, the
composition comprises:
(a) from about 10% to about 80%, by weight, a non-aqueous organic solvent
system; (b) from
about 5% to about 70%, by weight, sodium tripolyphosphate (STPP); (c) at least
about
0.00005%, by weight, a water-soluble dye; (d) an effective amount of water;
(e) from about 0.5%
to about 1%, by weight, a thickener; and (f) optionally an adjunct ingredient;
wherein the
composition is in the form of an anhydrous liquid gel; wherein the yield value
of the composition
has a range of from about 5 to about 35, preferably from about 10 to about 20,
more preferably
from about 12 to about 17, most preferably about 15; wherein the effective
amount of water is
calculated by the following formula: STPP + 6 H20 -~ STPP*6H20, and wherein
the
"STPP*6H2O" represents sodium tripolyphosphate hexahydrate.
In another aspect of the present invention, a method of cleaning soiled
tableware in an
automatic dishwashing machine is provided. In one non-limiting embodiment, the
method
comprises the step of washing the tableware in the presence of the organic
solvent composition
described above.
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
3
The following description can be provided to enable any person skilled in the
art to make
and use the invention, and can be provided in the context of a particular
application and its
requirements. Various modifications to the embodiments will be readily
apparent to those skilled
in the art, and the generic principles defined herein can be applied to other
embodiments and
applications without departing from the spirit and scope of the invention. The
present invention
is not intended to be limited to the embodiments shown. Thus, since the
following specific
embodiments of the present invention are intended only to exemplify, but in no
way limit, the
operation of the present invention, the present invention is to be accorded
the widest scope
consistent with the principles, features and teachings disclosed herein.
It should be understood that every maximum numerical limitation given
throughout this
specification will include every lower numerical limitation, as if such lower
numerical limitations
were expressly written herein. Every minimum numerical limitation given
throughout this
specification will include every higher numerical limitation, as if such
higher numerical
limitations were expressly written herein. Every numerical range given
throughout this
specification will include every narrower numerical range that falls within
such broader
numerical range, as if such narrower numerical ranges were all expressly
written herein.
All documents cited are, in relevant part, incorporated herein by reference;
the citation of
any document can be not to be construed as an admission that it can be prior
art with respect to
the present invention.
DETAILED DESCRIPTION OF THE INVENTION
DEFINITIONS
"Cloud point", as used herein, is a well known property of nonionic
surfactants which is
the result of the surfactant becoming less soluble with increasing
temperature, the temperature at
which the appearance of a second phase is observable is referred to as the
"cloud point" (See Kirk
Othmer, pp. 360-362).
"Detergent enzyme", as used herein, means any enzyme having a cleaning, stain
removing or otherwise beneficial effect in an organic solvent composition.
"Dishcare agent" means any type of composition or automatic dishwashing
detergent
additive that provides protective benefits to tableware during cleaning.
Dishcare agents can
include, but are not limited to, anti-corrosive agents, anti-tarnish agents,
silvercare agents, metal
care agents, and mixtures thereof.
"Tableware" means any type of dishware, glassware, cookware, and/or
silverware,
including, but not limited to, those made from glass, plastic, ceramic, metal,
wood, porcelain,
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
4
etc., as well as, any type of silverware which includes all types made from
metal, plastic, wood,
glass, ceramic, porcelain, etc. Tableware can include, but is not limited to,
cooking and eating
utensils, dishes, cups, bowls, glasses, silverware, pots, pans, etc.
ORGANIC SOLVENT COMPOSITION
Organic Solvent System
The cleaning of tableware can be carried out by the use of one or more organic
solvent
compositions (wherein "solvent composition" is understood to comprise the
organic solvent
system and optional additional active ingredients and diluents) and one or
more automatic
dishwashing detergent compositions. The organic solvent composition can be
built, unbuilt or
generally unbuilt. By "generally unbuilt" is meant that the composition
contains less than about
5% by weight of detergency co-builder.
A broad range of organic solvents are suitable for use herein but preferably
the organic
solvent is selected from alcohols, amines, esters, glycol ethers, glycols,
terpenes, and mixtures
thereof. The organic solvent system is preferably formulated to meet the
constraints on volatile
solvent components and in highly preferred, non-limiting embodiments the
organic solvent
system will contain from about 10% to about 80%, preferably from about 20% to
about 70%, and
more preferably from about 30% to about 50% of solvent components having a
vapor pressure
above about 0.1 mm Hg at 25°C at atmospheric pressure. In highly
preferred, non-limiting
embodiments, the solvent is essentially free (contains less than about, 5% by
weight) of solvent
components having a boiling point below about 150°C, flash point below
about 100°C or a vapor
pressure above about 1 mm Hg at 25°C at atmospheric pressure.
The organic solvents should be selected so as to be compatible with the
tableware, as
well as with, the different parts of an automatic dishwashing machine. The
individual organic
solvents used herein generally have a boiling point above about 150°C,
flash point above about
100°C and vapor pressure below about 1 mm Hg, preferably below 0.1 mm
Hg at 25°C at
atmospheric pressure.
Hansen solubility parameters were developed to characterize solvents for the
purpose of
comparison. Each of the three parameters (i.e., dispersion, polar and hydrogen
bonding)
represents a different characteristic of solvency. In combination, the three
parameters are a
measure of the overall strength and selectivity of a solvent. The above Hansen
solubility
parameter ranges identify solvents that are good solvents for a wide range of
substances and also
exhibit a degree of solubility in liquid carbon dioxide. The Total Hansen
solubility parameter,
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
which is the square root of the sum of the squares of the three parameters
mentioned previously,
provides a more general description of the solvency of the organic solvents.
In terms of solvent parameters, the organic solvent can be selected from (a)
polar,
hydrogen-bonding solvents having a Hansen solubility parameter of at least 20
(Mpa)1~2, a
polarity parameter of at least 7 (Mpa)l~z, preferably at least 12 (Mpa)1~z and
a hydrogen bonding
parameter of at least 10 (Mpa)1~2; (b) polar non-hydrogen bonding solvents
having a Hansen
solubility parameter of at least 20 (Mpa)1~2, a polarity parameter of at least
7 (Mpa)l~z, preferably
at least 12 (Mpa)1~2 and a hydrogen bonding parameter of less than 10
(Mpa)1~2; (c) amphiphilic
solvents having a Hansen solubility parameter below 20 (Mpa)l~z, a polarity
parameter of at least
7 (Mpa)1~2 and a hydrogen bonding parameter of at least 10 (Mpa)1~2; and (d)
non-polar solvents
having a polarity parameter below 7 (Mpa)1~z and a hydrogen bonding parameter
below 10
(Mpa)1~2, and mixtures thereof.
For example, solvents that can be used herein include: i) alcohols, such as
benzyl alcohol,
1,4-cyclohexanedimethanol, 2-ethyl-1-hexanol, furfuryl alcohol, 1,2-hexanediol
and other similar
materials; ii) amines, such as alkanolamines (e.g. primary alkanolamines:
monoethanolamine,
monoisopropanolamine, diethylethanolamine, ethyl diethanolamine; secondary
alkanolamines:
diethanolamine, diisopropanolamine, 2-(methylamino)ethanol; ternary
alkanolamines:
triethanolamine, triisopropanolamine); alkylamines (e.g. primary alkylamines:
monomethylamine, monoethylamine, monopropylamine, monobutylamine,
monopentylamine,
cyclohexylamine), secondary alkylamines: (dimethylamine), alkylene amines
(primary alkylene
amines: ethylenediamine, propylenediamine) and other similar materials; iii)
esters, such as ethyl
lactate, methyl ester, ethyl acetoacetate, ethylene glycol monobutyl ether
acetate, diethylene
glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and
other similar
materials; iv) glycol ethers, such as ethylene glycol monobutyl ether,
diethylene glycol
monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl
ether, diethylene
glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol
butyl ether and
other similar materials; v) glycols, such as propylene glycol, diethylene
glycol, hexylene glycol
(2-methyl-2, 4 pentanediol), triethylene glycol, composition and dipropylene
glycol and other
similar materials; and mixtures thereof.
The organic solvent system is preferably selected from i) glycol ethers, such
as ethylene
glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol
monomethyl ether,
ethylene glycol monoethyl ether, diethylene glycol monomethyl ether,
diethylene glycol
monoethyl ether, propylene glycol butyl ether and other similar materials; and
ii) glycols, such as
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
6
propylene glycol, diethylene glycol, hexylene glycol (2-methyl-2, 4
pentanediol), triethylene
glycol, composition and dipropylene glycol and other similar materials; and
mixtures thereof.
In one non-limiting embodiment, the automatic dishwashing detergent
composition is in
the form of a liquid gel comprising from about 10% to about 80%, preferably
from about 20% to
about 70%, most preferably from about 30% to about 50%, by weight, of a non-
aqueous organic
solvent, preferably dipropylene glycol.
Hydratable Builders
Phosphate Builder
Phosphate builders include, but are not limited to, the alkali metal, ammonium
and
alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates,
pyrophosphates, and glassy polymeric meta-phosphates). Phosphate builder
sources are
described in detail in Kirk Othmer, 3rd Edition, Vol. 17, pp. 426-472 and in
"Advanced Inorganic
Chemistry" by Cotton and Wilkinson, pp. 394-400 (John Wiley and Sons, Inc.;
1972).
A preferred phosphate builder salt is sodium tripolyphosphate (STPP). The STPP
can be
a blend of anhydrous STPP and a small amount of STPP hexahydrate such that the
chemically
bound water content corresponds to six H20 molecules per pentasodium
tripolyphosphate
molecule. Such STPP may be produced by treating anhydrous STPP with a limited
amount of
water. The presence of the hexahydrate slows down the rapid rate of solution
of the STPP in the
wash bath and inhibits caking. One suitable STPP is sold under the name
THERMPHOS~ NW.
The particles size of the THERMPHOS~ NW STPP, as supplied, is usually averages
200
microns with the largest particles being 400 microns.
One aspect of the invention relates to the use of hydrated STPP. The hydrated
STPP
used in one non-limiting embodiment of the present invention is preferably the
hexahydrate form.
Hydrated STPP is commercially available, however, it is expensive and
generally not completely
hydrated (e.g. it is only partially hydrated). A separate rehydration stage is
generally required as
a separate step in the process. Thus use of anhydrous STPP or partially
hydrated STPP in the
rehydration step is preferred. The effective amount of water in the organic
solvent composition is
determined by the amount of hexahydrate generated. The uptake of moisture
through the water-
soluble pouch containing the organic solvent composition is related to the
amount of water
present in the composition.
Since sodium tripolyphosphate hexahydrate is less readily soluble in water
than
potassium tripolyphosphate, the use of sodium tripolyphosphate hexahydrate is
preferred over
potassium tripolyphosphate. Sodium tripolyphosphate hexahydrate provides a
heterogeneous
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
7
character to the resulting gels giving a higher structural viscosity. This so-
called high structural
viscosity decreases considerably at relatively high spindle speeds and
increases considerably at
low spindle speeds. The viscosity measurements were carried out using a
ContravesTM rotational
cup & bob viscosimeter. The viscosities of the cleaning agents used in
accordance with the
invention extend up to 25,000 Pa.s, @ 1 s-1 as measured at a temperature of
25° C.
In one non-limiting embodiment of the present invention, sodium
tripolyphosphate is
typically present at a level of from about 5% to about 70% by weight,
preferably from about 7%
to about 50% by weight, most preferably from about 10% to about 30% by weight
of
composition.
Citrate Builder
Like phosphate builders, citrate builders are classified as sequestering
builders and
dissolve rapidly to form complexes with hardness ion. Although phosphate forms
much more
stable complexes with hardness ions, in regions where phosphate builders
cannot be used, citrate
builders are generally practiced.
Citrate builders include, but are not limited to, potassium and sodium salts
of citrate. A
preferred citrate builder is sodium citrate. One aspect of the invention
relates to the use of
hydrated sodium citrate, such that the chemically bound water content
corresponds to two H20
per sodium citrate molecule.
The hydrated sodium citrate used in one non-limiting embodiment of the present
invention is preferably the dihydrate form. Sodium citrate dihydrate, like
STPP hexahydrate,
provides a heterogeneous character to the resulting gels giving a higher
structural viscosity.
Since sodium citrate dihydrate is less soluble in water than the potassium
salt and does not form a
monohydrate like potassium citrate, the sodium salt is preferred over the
potassium salt.
In one non-limiting embodiment of the present invention, sodium citrate is
typically
present at a level of from about 5% to about 70% by weight, preferably from
about 7% to about
50% by weight, most preferably from about 10% to about 30% by weight of
composition.
Effective Amount of Water
The effective amount of water, preferably deionized water, in the anhydrous
organic
solvent composition of the present invention is determined by the amount of
hydrated builder
species to be generated. The uptake of moisture through the water-soluble
pouch containing the
anhydrous organic solvent composition is related to the amount of water
present in the
composition itself. For example, anhydrous solvent compositions generally
exhibit a higher
uptake of moisture than aqueous solvent compositions in water-soluble pouches.
Without being
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
8
bound by any particular theory, it is believed that water transportation
through the pouch wall can
be driven by a high gradient due to the presence of the source of alkalinity
(e.g. carbonate).
For example, the effective amount of water for the phosphate builder, STPP, is
calculated
by the following chemical equation: STPP + 6 H20 -~ STPP*6H20, wherein the
"STPP*6H20"
represents sodium tripolyphosphate hexahydrate. For example, if the
composition contains
22.37% STPP, the total amount of water needed to convert the STPP to 100%
STPP*6H20 is
6.57%. Note that some water will come from the stock material. If the stock
material is 20%
active, then 2.96% water is derived from the stock material alone. The balance
3.61% water will
be added to the composition to deliver a product yield value of from about 5
to about 10,
generally about 7.
Moisture Content
Comprehensive sets of analyses were completed on products comprising fully
anhydrous
organic solvent compositions. This anhydrous product was pouched in MONOSOL~
8630 PVA
film on the vertical heat sealer, placed in both sealed and un-sealed plastic
tubs with snap on lids,
and 100 pouches were placed in the following environments: 80°F/80%RH,
80°F/15% RH, and
Ambient (~70°F/26%RH). At the increments of 1, 2, 4, and 6 weeks the
following characteristics
were assessed: moisture content/pick-up, enzyme activity, pouch weight, pouch
feel, phase
stability, and relative pouch dissolution. Additionally girth-height
measurements of the pouches
were taken with modified calipers to obtain an indirect reading of the volume
changes due to
moisture pickup associated with the different environments under which the
pouches were
subjected. In addition, temperature and humidity were tracked throughout the
experiment via use
of HOBO~ data loggers.
As was seen in Table I below, the pouches at 80% relative humidity showed the
largest
average gain in weight (and >30% girth-height increase) after 6 weeks in
unsealed tubs.
Comparison of the results indicates that humidity is a large driver of the
weight change. Higher
humidity allows for more water pick-up, resulting in excessive pouch swelling
and consumer
dissatisfaction. Enzyme activities were also unacceptable at the higher
humidity.
TABLE
I
Ambient
70F, 26% Rel. 80F, 15% Rel. 80F, 80% Rel.
Humidity Humidity Humidity
Week % Weight Change % Weight Change % Weight Change
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
9
1 ~ 0.397% ~ 0.06% ~ 1.20%
2 0.529% 0.005% 2.11%
4 1.15% 0.44% 3.96%
6 1.52% ~ 1.49% ~ 5.96%
It has been surprisingly found that the present invention shows significantly
less weight
gain over the same period than the anhydrous compositions tested above. This
is believed to be
largely due to the use of hydrated STPP in the process. It is believed that
the co-builder, picks up
any free water and thus minimizes the swelling caused by excessive moisture
uptake during
unsealed storage.
Water-Soluble Dye
Readily water-soluble dyes or fluorescent brighteners are to be understood as
meaning
dyes or fluorescent brighteners having a solubility in water of >100
g/125° C. Suitable water-
soluble dyes are primarily textile dyes of all kinds of chemical classes. They
are for example
anionic dyes, such as nitro, aminoketone, ketone-imine, methine,
nitrodiphenylamine, quinoline,
aminonaphthaquinone or coumarin dyes or even acid dyes based on fustic
extract, in particular
acid anthraquinone and azo dyes, such as monoazo and disazo dyes. These dyes
contain at least
one anionic water-solubilizing group, for example a carboxyl or in particular
a sulfo group. The
dyes are generally in their salt form, for example in the form of the lithium,
sodium, potassium or
ammonium salt. Also possible are basic, i.e. cationic, dyes and stilbene dyes.
Examples thereof
are the halides, sulfates, methosulfates or metal halide salts, for example
tetrachlorozincates, of
azo dyes, such as monoazo, disazo and polyazo dyes, and of anthraquinone dyes,
phthalocyanine
dyes, diphenylinethane and triarylmethane dyes, methine, polymethine and
azomethine dyes and
of thiazole, ketone-amine, acridine, cyanine, nitro, quinoline, benzimidazole,
xanthene, azine,
oxazine and thiazine dyes. These basic dyes are commercially available under a
wide variety of
different names.
In one non-limiting embodiment of the present invention, the organic solvent
composition comprises at least 0.00005%, preferably at least 0.0005%, most
preferably at least
0.001% by weight of the total composition a water-soluble dye. Preferred water-
soluble dyes can
be selected from the group consisting of azo dye, stilbene dye, phthalocyanine
dye,
triphenodioxazine dye, formazan dye, anthraquinone dye, and mixtures thereof.
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
Thickener
Suitable thickening agents include inorganic clays (e.g. LAPONITE~, aluminium
silicate, bentonite, fumed silica), natural gum and cellulosic type
thickeners. The preferred clay
thickening agent can be either naturally occurring or synthetic. Preferred
synthetic clays include
the synthetic smectite-type clay sold under the trademark LAPONTTE~ by
Southern Clay
Products, Inc. Particularly useful are gel-forming grades such as LAPONITE RD~
and sol
forming grades such as LAPONITE RDS~. Natural occurring clays include some
smectite and
attapulgite clays. Mixtures of clays and polymeric thickeners are also
suitable for use herein.
Suitable natural gum thickeners include, for example, xanthan gum, locust bean
gum,
guar gum, and the like.
Preferred thickeners are the cellulosic type thickeners: hydroxyethyl and
hydroxymethyl
cellulose (ETHOCEL~ and METHOCEL~ available from Dow Chemical) can also be
used.
The compositions preferably are in liquid gel-form and contain a thickener
such as
methylcellulose or other nonionic cellulosic thickener.
ADJUNCT INGREDIENTS
Other Organic Solvents
The present invention includes the use of solvent compositions as additives
for
conventional automatic dishwashing detergent compositions. It also includes
multi-component
dishwashing products containing purpose-designated combination of solvent
compositions and
dishwashing detergent compositions. The invention also includes so called "all-
in-one" detergent
and cleaning products having both an alkaline detergent and a solvent
functionality. In the case
of additive and mufti-component products, the invention does not require the
two compositions to
be in the same physical form. The organic solvent composition can be in any
physical form, e.g.
liquid, paste, cream, gel, liquid gels and similarly the automatic dishwashing
detergent
composition can be in any of these forms. Preferably, however, both
compositions are in the
form of liquids and/or gels. The compositions used herein can be dispensed
from any suitable
device, such as bottles (pump assisted bottles, squeeze bottles), paste
dispensers, capsules, multi-
compartment bottles, mufti-compartment capsules, pouches, and mufti-
compartment pouches.
Pouches and mufti-compartment pouches are preferred. The solvent compositions
herein can
comprise one or more organic solvents and can additionally comprise
surfactant, bleach, enzyme,
enzyme stabilising components, etc.
The automatic dishwashing detergent (hereinafter "ADD") compositions herein
can
comprise traditional detergency components and can also comprise organic
solvents having a
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
11
cleaning function and organic solvents having a carrier or diluent function or
some other
specialised function. The compositions will generally be built and comprise
one or more
detergent active components which may be selected from colorants, bleaching
agents, surfactants,
alkalinity sources, enzymes, thickeners (in the case of liquid, paste, cream
or gel compositions),
anti-corrosion agents (e.g. sodium silicate), hydrotropes (e.g. sodium cumene
sulfate) and
disrupting agents. Highly preferred detergent components include a builder
compound, an
alkalinity source, a surfactant, an enzyme and a bleaching agent.
For example, liquid, gel or liquid gel ADD compositions of the present
invention can
contain water and other volatile solvents as carriers. Low quantities of low
molecular weight
primary or secondary alcohols such as methanol, ethanol, propanol and
isopropanol can be used
in the liquid detergent of the present invention. Other suitable carrier
solvents used in low
quantities includes glycerol, propylene glycol, ethylene glycol, 1,2-
propanediol, sorbitol, and
mixtures thereof.
Unless otherwise specified, the components described hereinbelow can be
incorporated
either in the organic solvent compositions and/or the ADD compositions.
Wettin~gent
The effect of the organic solvent system can be further improved by the
addition of
certain wetting agents. Preferably, the organic solvent system is used in
conjunction with a
wetting agent effective in lowering the surface tension of the organic solvent
system, preferably
to at least 1 mN/m less than that of the wetting agent, the wetting agent
preferably being selected
from organic surfactants having a surface tension less than about 30 mN/m,
more preferably less
than about 28 mN/m and specially less than about 26 mN/m. Preferred wetting
agents for use
herein are silicone polyether copolymers, especially silicone
poly(alkyleneoxide) copolymers
wherein alkylene is selected from ethylene, propylene, and mixtures thereof.
Source of Alkalinity
To provide an alkaline pH, the organic solvent composition comprises an
alkalinity
source. Generally, the alkalinity source raises the pH of the organic solvent
composition to at
least 10.0 in a 1 wt-% aqueous solution and preferably to a range of from
about 10.5 to 14. Such
pH is sufficient for soil removal and sediment breakdown when the chemical is
placed in use and
further facilitates the rapid dispersion of soils. The general character of
the alkalinity source is
limited only to those chemical compositions which have a substantial aqueous
solubility.
Exemplary alkalinity sources include an alkali metal silicate, hydroxide,
phosphate, or carbonate.
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
12
The alkalinity source can include an alkali metal hydroxide including sodium
hydroxide,
potassium hydroxide, lithium hydroxide, etc.
Mixtures of these hydroxide species can also be used. Alkaline metal silicates
can also
act as a source of alkalinity for the detergents of the invention. Useful
alkaline metal silicates
correspond with the general formula (MZO:SiOz) wherein for each mole of MZO
there is less than
one mole of Si02. Preferably for each mole of Si02 there is from about 0.2 to
about 100 moles of
M20 wherein M comprises sodium andlor potassium. Preferred sources of
alkalinity are alkaline
metal orthosilicate, alkaline metal metasilicate, and other well known
detergent silicate materials.
The alkalinity source can include an alkali metal carbonate. Alkali metal
carbonates that
may be used in the invention include sodium carbonate, potassium carbonate,
sodium and/or
potassium bicarbonate or sesquicarbonate, silicate, and mixtures thereof among
others. Preferred
carbonates include sodium and potassium carbonates. These sources of
alkalinity can be used the
detergents of the invention at concentrations about 0 wt-% to about 50 wt-%,
preferably from
about 5 wt-% to about 40 wt-%, and most preferably from about 10 wt-% to about
30 wt-%.
Co-Builder
All builders suitable for use in ADD compositions are suitable herein as co-
builders. The
co-builder of the present invention is typically present at a level of from
about 1 % to about 80%
by weight, preferably from about 10% to about 70% by weight, most preferably
from about 20%
to about 60% by weight of composition.
For example, the present invention may include, but are not limited to, the
following
builders: amorphous sodium silicates, aluminosilicates,
magnesioaluminosiliates, alkali metal,
phosphates, ammonium and alkanolammonium salts of polyphosphates (exemplified
by the
tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates),
phosphonates, phytic
acid, silicates, carbonates (including bicarbonates and sesquicarbonates),
sulfates, citrate, zeolite
and/or layered silicate, alkaline earth and alkali metal carbonates,
polycarboxylate compounds,
ether hydroxypolycarboxylates, copolymers of malefic anhydride with ethylene
or vinyl methyl
ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and
carboxymethyloxysuccinic acid,
the various alkali metal, ammonium and substituted ammonium salts of
polyacetic acids, such as
ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as
polycarboxylates, such as
mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene
1,3,5-tricarboxylic acid,
carboxymethyloxysuccinic acid, and soluble salts thereof, and citrate co-
builders, such as citric
acid and soluble salts thereof (particularly sodium salt).
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
'13
In one non-limiting embodiment of the present invention, the co-builder is
selected from
the group consisting of phosphate, phosphate oligomers or polymers and salts
thereof, silicate,
silicate oligomers or polymers and salts thereof, aluminosilicates,
magnesioaluminosiliates,
citrate, and mixtures thereof.
Enzyme
Preferred enzymes are hydrolases such as proteases, amylases and lipases.
Highly
preferred for automatic dishwashing are amylases and/or proteases, including
both current
commercially available types and improved types which, though more bleach
compatible, have a
remaining degree of bleach deactivation susceptibility.
The organic solvent compositions herein comprise one or more enzymes. If only
one
enzyme is used, it is preferably an amyolytic enzyme. Highly preferred for
automatic
dishwashing is a mixture of proteolytic enzymes and amyloytic enzymes. More
generally, the
enzymes to be incorporated include proteases, amylases, lipases, cellulases,
and peroxidases, as
well as mixtures thereof. Other types of enzymes may also be included. They
may be of any
suitable origin, such as vegetable, animal, bacterial, fungal and yeast
origin. However, their
choice is governed by several factors such as pH-activity and/or stability
optima, thermostability,
stability versus active detergents, co-builders, etc. In this respect
bacterial or fungal enzymes are
preferred, such as bacterial amylases and proteases, and fungal cellulases.
Enzymes are normally incorporated in the instant detergent compositions at
levels
sufficient to provide a "cleaning-effective amount". The term "cleaning-
effective amount" refers
to any amount capable of producing a cleaning, stain removal or soil removal
effect on substrates
such as fabrics, dishware and the like. Since enzymes are catalytic materials,
such amounts may
be very small.
In practical terms for current commercial preparations, typical amounts are up
to about 5
mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per
gram of the
composition. Protease enzymes are usually present in such commercial
preparations at levels
sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram
of composition,
preferably 0.01%-1% by weight of a commercial enzyme preparation.
Enzyme-containing compositions, especially liquid, liquid gel and gel
compositions,
herein may comprise from about 0.0001% to about 10%, preferably from about
0.005% to about
8%, most preferably from about 0.01% to about 6%, by weight of an enzyme
stabilizing system.
The enzyme stabilizing system can be any stabilizing system which is
compatible with the
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
14
detersive enzyme. Such stabilizing systems can comprise calcium ion, boric
acid, propylene
glycol, short chain carboxylic acid, boronic acid, and mixtures thereof.
For automatic dishwashing purposes, it may be desirable to increase the active
enzyme
content of the commercial preparations, in order to minimize the total amount
of non-catalytically
active materials delivered and thereby improve spotting/filming results.
In a non-limiting embodiment of the present invention, the organic solvent
composition
comprises from about 0.0001 % to about 2% by weight of the total composition,
an enzyme
stabilizing system.
Surfactant
In compositions and methods of the present invention for use in automatic
dishwashing
the detergent surfactant is preferably low foaming by itself or in combination
with other
components (i.e. suds suppressers). In compositions and methods of the present
invention for use
in cleaning soiled tableware prior to dishwashing, the detergent surfactant is
preferably foamable
in direct application but low foaming in automatic dishwashing use.
Surfactants suitable herein include anionic surfactants such as alkyl
sulfates, alkyl ether
sulfates, alkyl benzene sulfonates, alkyl glyceryl sulfonates, alkyl and
alkenyl sulphonates, alkyl
ethoxy carboxylates, N-acyl sarcosinates, N-acyl taurates and alkyl succinates
and
sulfosuccinates, wherein the alkyl, alkenyl or acyl moiety is CS-C20 ,
preferably C10-Clg linear
or branched; cationic surfactants such as chlorine esters (US-A-4228042, US-A-
4239660 and
US-A-4260529) and mono C6-C16 N-alkyl or alkenyl ammonium surfactants wherein
the
remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl
groups; low and
high cloud point nonionic surfactants, and mixtures thereof including nonionic
alkoxylated
surfactants (especially ethoxylates derived from C6-Clg primary alcohols),
ethoxylated-
propoxylated alcohols (e.g., Olin Corporation's Poly-Tergent~ SLF18), epoxy-
capped
poly(oxyalkylated) alcohols (e.g., Olin Corporation's Poly-Tergent~ SLF18B -
see WO-A-
94/22800), ether-capped poly(oxyalkylated) alcohol surfactants, and block
polyoxyethylene-
polyoxypropylene polymeric compounds such as PLURONIC~, REVERSED PLURONIC~,
and
TETRONIC~ by the BASF-Wyandotte Corp., Wyandotte, Michigan; amphoteric
surfactants
such as the C12-Coo alkyl amine oxides (for example, amine oxides for use
herein include
lauryldimethyl amine oxide and hexadecyl dimethyl amine oxide), and alkyl
amphocarboxylic
surfactants such as MiranolTM C2M; and zwitterionic surfactants such as the
betaines and
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
sultaines; and mixtures thereof. Surfactants suitable herein are disclosed,
for example, in US-A-
3,929,678 , US-A- 4,259,217, EP-A-0414 549, WO-A-93/08876 and WO-A-93/08874.
Surfactants are typically present at a level of from about 0.2% to about 30%
by weight,
more preferably from about 0.5% to about 10% by weight, most preferably from
about 1% to
about 5% by weight of composition.
In one non-limiting embodiment of the present invention, the organic solvent
composition comprises from about 0% to about 30% by weight, a surfactant
selected from the
group consisting of anionic surfactants, cationic surfactants, nonionic
surfactants, amphoteric
surfactants, ampholytic surfactants, zwitterionic surfactants; and mixtures
thereof. In another
non-limiting embodiment of the present invention, the surfactant is amine
oxide at a level of
about 0.5% to about 20%, by weight.
Suds Su~pressor
Preferred surfactants for use herein are low foaming and include low cloud
point
nonionic surfactants and mixtures of higher foaming surfactants with low cloud
point nonionic
surfactants which act as suds suppressors therein (see WO-93/08876 and EP-A-
0705324).
Typical low cloud point nonionic surfactants which act as suds suppressors
include
nonionic alkoxylated surfactants, especially ethoxylates derived from primary
alcohol, and
polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block
polymers.
Also, such low cloud point nonionic surfactants include, for example,
ethoxylated-propoxylated
alcohol (e.g., Olin Corporation's POLY-TERGENT~ SLF18) and epoxy-capped
poly(oxyalkylated) alcohols (e.g., Olin Corporation's POLY-TERGENT~ SLF18B
series of
nonionics, as described, for example, in US-A-5,576,281).
Preferred low cloud point surfactants are the ether-capped poly (oxyalkylated)
suds
suppressor having the formula:
R1G-( CH2 - i H -O)X - (CH2 -CH2 -O~ - (CH2 - i H-O)z-H
R2 R3
wherein R1 is a linear, alkyl hydrocarbon having an average of from about 7 to
about 12 carbon
atoms, RZ is a linear, alkyl hydrocarbon of about 1 to about 4 carbon atoms,
R3 is a linear, alkyl
hydrocarbon of about 1 to about 4 carbon atoms, x is an integer of about 1 to
about 6, y is an
integer of about 4 to about 15, and z is an integer of about 4 to about 25.
Other low cloud point nonionic surfactants are the ether-capped
poly(oxyalkylated)
having the formula:
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
16
RIO(Ra0)nCH(CH3)OR~
wherein, RI is selected from the group consisting of linear or branched,
saturated or unsaturated,
substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals
having from about 7 to
about 12 carbon atoms; Ra may be the same or different, and is independently
selected from the
group consisting of branched or linear CZ to C~ alkylene in any given
molecule; n is a number
from 1 to about 30; and R~ is selected from the group consisting of:
(i) a 4 to 8 membered substituted, or unsubstituted heterocyclic ring
containing from 1
to 3 hetero atoms; and
(ii) linear or branched, saturated or unsaturated, substituted or
unsubstituted, cyclic or
acyclic, aliphatic or aromatic hydrocarbon radicals having from about 1 to
about 30
carbon atoms;
provided that when RZ is (ii) then either: (A) at least one of Rl is other
than CZ to C3 alkylene; or
(B) Rz has from 6 to 30 carbon atoms, and with the further proviso that when
R2 has from 8 to 18
carbon atoms, R is other than Cl to C5 alkyl.
Suds suppressors are typically present at a level of from about 0.2% to about
30% by
weight, more preferably from about 0.5% to about 10% by weight, most
preferably from about
1% to about 5% by weight of composition.
Bleaching System
In one non-limiting embodiment of the present invention a bleaching system
comprises a
bleach, a bleach catalyst, a bleach activator, and mixtures thereof. In a non-
limiting embodiment
of the present invention, the organic solvent composition comprises a
bleaching system in an
amount from about 0% to about 15%, preferably from about 1% to about 10%, more
preferably
from about 2% to about 6% by weight of the total composition.
Bleaching agents suitable herein include chlorine and oxygen bleaches,
especially
inorganic perhydrate salts such as sodium perborate mono-and tetrahydrates and
sodium
percarbonate optionally coated to provide controlled rate of release (see, for
example, GB-A-
1466799 on sulfate/carbonate coatings), preformed organic peroxyacids, and
mixtures thereof
with organic peroxyacid bleach precursors and/or transition metal-containing
bleach catalysts
(especially manganese or cobalt).
Peroxygen bleaching compounds can be any peroxide source, and is preferably a
member
selected from the group consisting of sodium perborate monohydrate, sodium
perborate
tetrahydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium
percarbo- nate,
sodium peroxide and mixtures thereof. Highly preferred peroxygen bleaching
compounds are
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
17
selected from the group consisting of sodium perborate monohydrate, sodium
perborate
tetrahydrate, sodium percarbonate and mixtures thereof.
Bleach catalysts preferred for use herein include the manganese
triazacyclononane and
related complexes (US-A-4246612, US-A-5227084); Co, Cu, Mn and Fe
bispyridylamine and
related complexes (US-A-5114611); and pentamine acetate cobalt(IlI) and
related complexes(US-
A-4810410) at levels from 0% to about 10.%, by weight; preferably from 0.1 %
to 1.0%.
Typical bleach activators preferred for use herein include peroxyacid bleach
precursors,
precursors of perbenzoic acid and substituted perbenzoic acid; cationic
peroxyacid precursors;
peracetic acid precursors such as TAED, sodium acetoxybenzene sulfonate and
pentaacetylglucose; pernonanoic acid precursors such as sodium 3,5,5-
trimethylhexanoyloxybenzene sulfonate (iso-NOBS) and sodium nonanoyloxybenzene
sulfonate
(NOBS); amide substituted alkyl peroxyacid precursors (EP-A-0170386); and
benzoxazin
peroxyacid precursors (EP-A-0332294 and EP-A-0482807) at levels from 0% to
about 10.%, by
weight; preferably from 0.1% to 1.0%.
Other bleach activators include to substituted benzoyl caprolactam bleach
activators and
their use in bleaching systems and laundry detergents. The substituted benzoyl
caprolactaxns
have the formula:
R1
O C-CHZ CH2~
R I I I CH2
R3 C-N~CH2-CH ~
'R5
R4
wherein R1, R2, R3, R4, and R5 contain from 1 to 12 carbon atoms, preferably
from 1 to 6
carbon atoms and are members selected from the group consisting of H, halogen,
alkyl, alkoxy,
alkoxyaryl, alkaryl, alkaryloxy, and members having the structure:
O O O O
II ~~ II II
-X-C-R6, C-N-R7, and -C-N-C
R8 Ra
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
1~3
wherein R6 is selected from the group consisting of H, alkyl, alkaryl, alkoxy,
alkoxyaryl,
alkaryloxy, and aminoalkyl; X is O, NH, or NR7, wherein R7 is H or a C1-C4
alkyl group; and
Rg is an alkyl, cycloalkyl, or aryl group containing from 3 to 11 carbon
atoms; provided that at
least one R substituent is not H.
In a non-limiting embodiment, R1, R2, R3, and R4 are H and R5 is selected from
the
group consisting of methyl, methoxy, ethyl, ethoxy, propyl, propoxy,
isopropyl, isopropoxy,
butyl, tert-butyl, butoxy, tert-butoxy, pentyl, pentoxy, hexyl, hexoxy, Cl,
and N03. In another
preferred embodiment, R1, R2, R3 are H, and R4 and R5 are members selected
from the group
consisting of methyl, methoxy, and Cl.
In a non-limiting embodiment of the present invention the bleaching system
comprises:
a) from about 0% to about 15% by weight, preferably from about 2% to about 6%
by weight, of
a peroxygen bleaching compound capable of yielding hydrogen peroxide in an
aqueous solution;
b) from about 0% to about 1.0% by weight, of one or more substituted benzoyl
caprolactam
bleach activators having the formula:
R1
O C-CH2-CHZ~CH2
R
R3 C-N ~CH~ CH2
'RS
R4
wherein R1, R2, R3, R4, and R5 are as defined above.
Other Suitable Components
In another embodiment of the present invention, the organic solvent
composition can
further comprise antiredopsition agents, free radical inhibitors, polymers,
soil release agents, anti-
filming agents, anti-spotting agents, hydrotropes, germicides, fungicides,
color speckles, bleach
scavengers, dishcare agents, and mixtures thereof
The compositions herein can contain a corrosion inhibitor such as organic
silver coating
agents in levels of from about 0.05% to about 10%, preferably from about 0.1%
to about 5% by
weight of composition (especially paraffins such as Winog 70 sold by
Wintershall, Salzbergen,
Germany), nitrogen-containing corrosion inhibitor compounds (for example
benzotriazole and
benzimadazole - see GB-A-1137741) and Mn(II) compounds, particularly Mn(II)
salts of organic
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
19
ligands in levels of from about 0.005 % to about 5 %, preferably from about
0.01 % to about 1 %,
more preferably from about 0.02% to about 0.4% by weight of the composition.
Organic polymers having dispersant, anti-redeposition, soil release or other
detergency
properties can exist in the present invention at levels of from about 0.1 % to
about 30%,
preferably from about 0.5% to about 15%, most preferably from about 1% to
about 10% by
weight of composition. Preferred anti-redeposition polymers herein include
acrylic acid
containing polymers such as Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10
(BASF
GmbH), Acusol 45N, 480N, 460N (Rohm and Haas), acrylic acid/maleic acid
copolymers such as
Sokalan CP5 and acrylic/methacrylic copolymers. Preferred soil release
polymers herein include
alkyl and hydroxyalkyl celluloses (US-A-4,000,093), polyoxyethylenes,
polyoxypropylenes and
copolymers thereof, and nonionic and anionic polymers based on terephthalate
esters of ethylene
glycol, propylene glycol, and mixtures thereof.
Heavy metal sequestrants and crystal growth inhibitors are suitable for use
herein in
levels generally from about 0.005% to about 20%, preferably from about 0.1% to
about 10%,
more preferably from about 0.25% to about 7.5% and most preferably from about
0.5% to about
5% by weight of composition, for example diethylenetriamine penta (methylene
phosphonate),
ethylenediamine tetra(methylene phosphonate) hexamethylenediamine
tetra(methylene
phosphonate), ethylene diphosphonate, hydroxy-ethylene-1,1-diphosphonate,
nitrilotriacetate,
ethylenediaminotetracetate, ethylenediamine-N,N'-disuccinate in their salt and
free acid forms.
Other suitable components herein include water-soluble bismuth compounds such
as
bismuth acetate and bismuth citrate at levels of from about 0.01% to about 5%,
enzyme
stabilizers such as calcium ion, boric acid, propylene glycol and chlorine
bleach scavengers at
levels of from about 0.01% to about 6%, lime soap dispersants (see WO-A-
93/08877), colorants,
optical brighteners, perfumes, fillers and clay.
METHOD OF USE
The invention can be applied to single-phase "all-in-one" products. According
to this
aspect, a method of cleaning soiled tableware comprises washing the tableware
in an automatic
dishwashing machine with an automatic dishwashing detergent composition
comprising
surfactant (preferably comprising low-foaming nonionic surfactant), detergency
co-builder and
organic solvent system in levels sufficient to provide a wash liquor
concentration of from about
ppm to about 1000 ppm surfactant, from about 100 ppm to about 5000 ppm
detergency co-
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
builder, and about 100 ppm to about 10,000, preferably from about 500 ppm to
about 5000 ppm
of organic solvent.
In another embodiment of the invention the organic solvent composition can be
in a unit
dose form allowing controlled release (for example delayed, sustained,
triggered or slow release)
of the composition during one or more repeated washing cycles. In preferred
unit dose forms, the
solvent composition is contained in a single or mufti-compartment water-
soluble pouch.
ARTICLE OF MANUFACTURE
The invention also relates to an article of manufacture comprising (a) a
package, (b)
instructions for use, and (c) an organic solvent composition suitable for use
in automatic
dishwashing comprising (i) from about 10% to about 80% by weight of an organic
solvent
system, ii) from about 5% to about 70% by weight of STPP; at least about
0.00005% by weight
of a water-soluble dye; iii) an effective amount of water; iv) optionally, an
adjunct ingredient;
wherein the composition is in the form of an anhydrous liquid, paste, cream or
gel.
Water-soluble Pouch
It is a feature of the invention that many of the organic solvent systems and
compositions
of the invention that are optimum for cleaning also demonstrate improved
compatibility with
partially hydrolysed, water-soluble PVA pouch materials of known construction
and type. This is
particularly surprising given that many well-known polar/or hydrolysed bonding
solvent materials
(for example the organoamines) in themselves have low compatibility with PVA
materials and
present serious issues for product stability.
The organic solvent composition can be in any physical form, e.g. liquid,
paste, cream,
gel, liquid gels and similarly the automatic dishwashing detergent composition
can be in any of
these forms. Preferably, however, both compositions are in the form of
liquids, liquid gels and/or
gels. The compositions used herein can be dispensed from any suitable device,
such as bottles
(pump assisted bottles, squeeze bottles), paste dispensers, capsules, mufti-
compartment bottles,
mufti-compartment capsules, and single- and mufti-compartment water-soluble
pouches. Single-
and mufti-compartment water-soluble pouches are preferred. In the case of
additive and multi-
component products, the invention does not require the two compositions to be
in the same
physical form.
EXAMPLES
TABLE II
CA 02496227 2005-02-18
WO 2004/018611 PCT/US2003/026270
21
1 I 2
Material Weight % Weight %
Hydrated Intermediate Powder
- STPP I 22.37 I 29.63
- DI Water ~ 3.61 ~ 4.78
Finished Product
- Dipropylene Glycol 38.38 0.00
- SLF-18 4.63 4.00
- C14 Amine Oxide 3.70 3.00
- DI Water ~ 0.00 ~ 37.99
- G100 Sodium Carbonate ~ 21.80 ~ 16.46
- Hydrated Intermediate Powder ~ 25.98 ~ 34.41
- Britesil H20 1.41 1.41
- BHT 0.00 0.10
- Methocel OS Thickener 0.20 0.03
Sodium Perborate Monohydrate ~ 0.00 ~ 0.00
- LiquiBlu 4 Perfume ~ 0.16 ~ 0.16
- Direct Blue 86 Soln I 0.14 I 0.14
- FN3 Enzyme Slurry I 1.60 I 1.39
- Natalase Enzyme Prill I 2.00 I 0.91
TOTAL I 100.00 I 100.00
